Alkylation process



United States Patent 01 Patented Jan. 7, 1969 lice 3,420,909 ALKYLATIONPROCESS Louis Schmerling, Riverside, lll., assignor to Umversal OilProducts Company, Des Plaines, 11]., a corporation of Delaware NoDrawing. Filed Aug. 21, 1967, Ser. No. 661,776 US. Cl. 260-671 8 ClaimsInt. Cl. C07c 3/56 ABSTRACT OF THE DISCLOSURE An alkylatable aromatichydrocarbon is alkylated with a saturated hydrocarbon utilizing acatalyst comprising aluminum chloride and the higher-valence halide of ametal which forms at least two metal halides differing in valence.

Description of the invention This invention relates to a conversionprocess for the alkylation of alkylatable aromatic hydrocarbons intomore useful compounds. More specifically, this invention is concernedwith a conversion process for the alkylation of an alkylatable aromatichydrocarbon with a saturated hydrocarbon utilizing a novel catalystcomprising aluminum chloride and the higher-valence halide of a metalwhich forms at least two metal halides differing in valence.

It is, therefore, an object of this invention to provide a process forthe alkylation of alkylatable aromatic hydrocarbons utilizing a novelalkylation catalyst.

A specific object of this invention is to provide a novel method and anovel catalyst for alkylating alkylatable aromatic hydrocarbons toprovide the desired alkylated product in high yields.

One embodiment of the invention relates to a process for the alkylationof an alkylatable aromatic hydrocarbon with a saturated hydrocarbon atalkylation conditions in the presence of a catalyst comprising aluminumchloride and the higher-valence halide of a metal which forms at leasttwo metal halides differing in valence.

A second embodiment of this invention relates to a process for thealkylation of an alkylatable benzene hydrocarbon with a saturatedhydrocarbon at alkylation conditions including a temperature in therange of about to about 200 C. and a pressure in the range of from aboutatmospheric to about 200 atmospheres in the presence of a catalystcomprising aluminum chloride and the higher-valence halide of a metalwhich forms at least two metal halides differing in valence.

The process of my invention is applicable to the alkylatable aromatichydrocarbons including, for example, benzene, toluene, ortho-Xylene,meta-xylene, para-xylene, ethylbenzene, ortho-ethyltoluene,meta-ethyltoluene, paraethyltoluene, 1,2,3-trimethylbenzene,1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, diethylbenzene,triethylbenzene, normal propylbenzene, isopropylbenzene, etc., andmixtures thereof. Preferred alkylatable aromatic hydrocarbons arebenzene and monoalkylated benzenes. Higher molecular weight alkylaromatic hydrocarbons are suitable. These include those aromatichydrocarbons such as are produced by the alkylation of aromatichydrocarbons with olefin polymers and are used as intermediates in thepreparation of sulfonate surface-active agents. Such products includehexylbenzenes, nonylbenzene, dodecylbenzenes, pentadecylbenzenes,hexyltoluenes, nonyltoluenes, dodecyltoluenes, pentadecyltoluenes, etc.Very often, the product is obtained as a high boiling fraction in whichthe alkyl group attached to the aromatic nucleus varies in size fromabout 0,, to C Other suitable aromatic hydrocarbons, which at specifiedconditions, depending upon the melting point of the aromatic chosen,would be in liquid form, Would include those aromatic hydrocarbons withtwo or more aryl groups such as diphenyl, diphenylmethane, triphenyl,triphenylmethaue, fiuorene, stilbene, etc. Examples of other aromatichydrocarbons utilizable in the scope of this invention which, becausethey may be normally solid at the alkylation conditions, are alkylatedin a solvent, preferably an excess of the saturated hydrocarbon, includethose containing condensed aromatic rings. These include naphthalenes,alkylnaphthalenes, anthracene, phenanthrene, naphthacene, rubrene, etc.Of the above-mentioned aromatic hydrocarbons that could be utilized inthe process of this invention, the benzene hydrocarbons are preferred,and of the preferred benzene hydrocarbons, benzene itself isparticularly preferred.

The saturated hydrocarbons, acting as the alkylating agent, may beselected from diverse materials including the acyclic paraflinhydrocarbons and cycloparaflin hydrocarbons are the alkanes andcycloalkanes containing tertiary carbon atoms. Other suitable alkylatingagents include normal butane, normal pentane, isopentane, normal hexane,isohexane, normal heptane, Z-methylhexane, normal octane, etc. Suitablecycloalkanes such as the cyclopentanes and cyclohexanes, includingcyclopentane, methylcyclopentane, dimethylcyclopentanes, cyclohexane,methylcyclohexane, dimethylcyclohexanes, etc. Mixtures of saturatedhydrocarbons may also be utilized.

As hereinabove set forth, the invention is concerned with a process forthe alkylation of alkylatable aromatic hydrocarbons, said process beingeffected by the presence of a catalyst which possesses a high degree ofhydrocarbon conversion activity and is particularly effective as analkylation catalyst for alkylatable aromatic hydrocarbons. The catalystcomprises aluminum chloride and a highervalence halide of a metal whichforms at least two metal halides differing in valence. Suitable metalswhich form at least two metal halides ditfering in valence includecopper, mercury, iron, tin, cobalt, molybdenum, manganese, and chromium.The various bromides and chlorides of the above metals includingmercuric chloride, mercuric bromide, cupric chloride, cupric bromide,ferric chloride, ferric bromide, stannic chloride, stannic bromide,cobaltic chloride, cobaltic bromide, molybdenum trichloride, molybdenumtetrachloride, molybdenum tetrabromide, molybdenum pentabromide,manganese trichloride, manganese tribromide, chromic chloride, chromicbromide, etc., are thus utilizable in the scope of my invention.

A particularly preferred catalyst for use in the process of thisinvention is the catalyst comprising aluminum chloride and cupricchloride. The aluminum chloride may be used in a catalytic amount, orpreferably, in equimolar amounts with the cupric chloride. The chloridesmay be added separately or as a complex, Al Cl -CuCl- The process ofthis invention utilizing the catalyst hereinbefore set forth may beeffected in any suitable manner and may comprise either a batch or acontinuous type operation. The preferred method by which the process ofthis invention may be effected is a continuous type operation. Oneparticular method is the operation in which the alkylatable aromatichydrocarbon and the saturated hydrocarbon are continuously charged to areaction zone containing the desired catalyst, said zone beingmaintained at the proper operating conditions of temperature andpressure, that is, a temperature in the range of from about 0 to about200 C. and preferably a temperature of from about 20 to about C., and apressure including a pressure of from about atmospheric to about 200atmospheres or more. The rate at which the hydrocarbon charge is addedmay be varied within a relatively Wide range. The reaction zone maycomprise an unpacked vessel or coil or may contain a packing material.The two reactants may be charged through separate lines, or, if sodesired, may be admixed prior to entry into said reaction zone andcharged thereto in a single stream. This charge passes into the reactionzone containing the catalyst in an upward, downward, or radial flow andthe alkylated product is continuously withdrawn, separated from thereactor etfiuent and recovered, while any other unreacted startingmaterial may be recycled to form a portion of the feed stock. Anothercontinuous type operation comprises the moving bed type in which thereactants and the catalyst move either concurrently or countercurrentlyto each other while passing through said reaction zone.

Still another type operation which may be used in the batch typeoperation in which a quantity of the alkylatable aromatic hydrocarbon,the saturated hydrocarbon and the catalyst are placed in an appropriateapparatus such as, for example, a rotating or stirred autoclave. Theapparatus is then maintained at the desired temperature for apredetermined residence time at the end of which time the flask andcontents thereof are cooled to room temperature (it a higher reactionwas employed) and the desired reaction product is recovered byconventional means, such as, for example, by washing, drying, fractionaldistillation, crystallization, etc.

The following examples are introduced for the purpose of illustrationonly with no intention of unduly limiting the broad scope of the presentinvention.

Example I In this example, 20 grams (0.2 mole) of benzene and 24 grams(0.33 mole) of isopentane were stirred and mixed at room temperaturewith 22 grams of catalyst In this example, 46.5 grams (0.5 mole) oftoluene and 53 grams (0.62 mole) of 2,3-dimethylbutane were mixed andstirred at 25-27 C. with a catalyst comprising alu- 4 minum chloride andcupric chloride. The vigorous evolution of HCl was noted. The productwas subsequently treated with ice water followed by ether extraction anda product containing two hexylbenzene isomers including2-phenyl-2,3-dimethylbutane and 2-phenyl-3,3-dimethylbutane wasrecovered.

I claim as my invention:

1. A process for the alkylation of an alkylatable aromatic hydrocarbonwith a saturated hydrocarbon at alkylation conditions in the presence ofa catalyst comprising aluminum chloride and a higher-valence halide of ametal which forms at least two metal halides differing in valence.

2. Theprocess of claim 1 further characterized in that said alkylatablearomatic hydrocarbon is a benzene hydrocarbon.

3. The process of claim 1 further characterized in that said saturatedhydrocarbon is an acyclic paraffin hydrocarbon.

4. The process of claim 1 further characterized in that said saturatedhydrocarbon is a cycloparafiin hydrocarbon.

5. The process of claim 1 further characterized in that said alkylationconditions include a temperature in the range of from about 0 to about200 C. and a pressure in the range of from about atmospheric to about200 atmospheres.

6. The process of claim 1 further characterized in that said metal whichforms at least two metal halides differing in valence is copper and thatsaid halide of the metal is chloride.

7. The process of claim 6 further characterized in that said benzenehydrocarbon is benzene and that said saturated hydrocarbon isisopentane.

8. The process of claim 6 further characterized in that said benzenehydrocarbon is toluene and that said saturated hydrocarbon is2,3-dimethylbutane.

References Cited UNITED STATES PATENTS 2,304,290 12/1942 Van Peski .a260671 2,426,665 9/1947 Bloch 260-671 2,433,020 12/1947 Becker 260-6713,109,038 10/1963 Myers 260671 DELBERT E. GANTZ, Primary Examiner.

C. R. DAVIS, Assistant Examiner.

